Thermochemistry Chapter 6 and 17 AP Chemistry

thermodynamics: the study of energy and its transformations -- thermochemistry: the subdiscipline involving chemical reactions and energy changes

temperature. Energy kinetic energy: energy of motion; KE = ½ mv 2 -- all particles have KE -- Thermal energy is due to the KE of particles. We measure the average KE of a collection of particles as... potential energy: stored energy Chemical potential energy is due to electrostatic forces between charged particles. -- related to the specific arrangement of atoms in the substance ++

Units of energy are joules (J), kilojoules (kJ), calories (cal), or nutritional calories (Cal or kcal). -- conversions: James Prescott Joule ( ) SI unit 4184 J = kJ = 1000 cal = 1 Cal = 1 kcal

system: the part of the universe we are studying surroundings: everything else -- In chemistry, a closed system can exchange energy but not matter with its surroundings. -- Usually, energy is transferred to... …(1)...or...(2) change an object’s state of motion cause a temperature change

Work (w) is done when a force moves through a distance. W = F d Heat (q) is an amount of energy transferred from a hotter object to a colder one.

Find the kinetic energy of a single dinitrogen monoxide molecule moving at 650 m/s. N2ON2O(laughing gas) KE = ½ mv 2 m = 44 amu = 7.31 x 10 –26 kg KE = ½ (7.31 x 10 –26 kg) (650 m/s) 2 = 1.5 x 10 –20 J ?

First Law of Thermodynamics Law of Conservation of Energy = -- Energy morphs between its various forms, but the total amount remains the same. (pretty much)

In endothermic processes, heat is _________ by the system. e.g., absorbed melting boiling sublimation e.g., released freezing condensation deposition In exothermic processes, heat is ________ by the system.

Exothermic process is any process that gives off heat – transfers thermal energy from the system to the surroundings. 2H 2 (g) + O 2 (g) 2H 2 O (l) + energy H 2 O (g) H 2 O (l) + energy Endothermic process is any process in which heat has to be supplied to the system from the surroundings. energy + 2HgO (s) 2Hg (l) + O 2 (g) energy + H 2 O (s) H 2 O (l)

> internal energy (E) of a system: the sum of all the KE and PE of the components of a system -- The change in the internal energy of a system would be found by: ΔE = E final – E initial And for chemistry, this equation would become: ΔE = E products – E reactants ΔE is + if E final E initial (i.e., system... ) ΔE is – if E final E initial (i.e., system... ) < gains energy loses energy → ENDOTHERMIC → EXOTHERMIC

But we ARE able to find ΔE by measuring two types of “energy” quantities: ΔE = q + w q = heat: +/– q = system absorbs/releases heat w = work: +/– w = work done on/by system ** KEY: Sign conventions are based on the system’s point of view.

To go further, we must introduce the concept of enthalpy (H). -- Enthalpy (H) is defined as...H = E + PV whereE = system’s internal energy P = pressure of the system V = volume of the system Heike Kamerlingh Onnes 1853–1926 The Dutch physicist and Nobel laureate H.K. Onnes coined the term enthalpy, basing it on the Greek term enthalpein, which means “to warm.”

ΔH = H final – H initial = q P P indicates constant pressure conditions. When ΔH is +, the system... has gained heat. When ΔH is –, the system...has lost heat. Enthalpy is an extensive property, meaning that… (ENDO) (EXO) Enthalpy is used to quantify the heat that is either gained or lost by a system that Is at constant pressure. the amount of material affects its value.

In the burning of firewood at constant pressure, the enthalpy change equals the heat released. ΔH is (–) and depends on the quantity of wood burned.

For exothermic rxns, the heat content of the reactants is larger than that of the products. enthalpy of reaction: ΔH rxn = H products – H reactants (also called “heat of reaction”)

ΔH = –2390 kJ 2 H 2 (g) + O 2 (g) → 2 H 2 O(g)ΔH = –483.6 kJ What is the enthalpy change when 178 g of H 2 O are produced? 178 g H 2 O The space shuttle was powered by the reaction above.

ΔH for a reaction and its reverse are the opposites of each other. Enthalpy change depends on the states of reactants and products. 2 H 2 (g) + O 2 (g)2 H 2 O(g)(ΔH = –483.6 kJ) 2 H 2 O(g) 2 H 2 (g) + O 2 (g)(ΔH = kJ) Enthalpy/energy is a reactant. 2 H 2 (g) + O 2 (g)2 H 2 O(g)(ΔH = –483.6 kJ) 2 H 2 (g) + O 2 (g)2 H 2 O(l)(ΔH = –571.6 kJ)

Calorimetry: the measurement of heat flow -- device used is called a...calorimeter heat capacity of an object: amount of heat needed to raise object’s temp. 1 K = 1 o C molar heat capacity: amt. of heat needed to raise temp. of 1 mol of a substance 1 K specific heat (capacity): amt. of heat needed to raise temp. of 1 g of a substance 1 K i.e., molar heat capacity = molar mass X specific heat

c X = heat of fusion (s/l) or heat of vaporization (l/g) We calculate the heat a substance loses or gains using: where q = heat m = amount of substance c P = substance’s heat capacity ΔT = temperature change q = m c P ΔT (for within a given state of matter) AND q = + / – m c X (for between two states of matter)

HEA T Temp. s s/l l l/g g heat added (+q) → ← heat removed (–q) Typical Heating Curve

What is the enthalpy change when 679 g of water at 27.4 o C are converted into water vapor at o C? HEAT Temp. s s/l l l/g g q = m c P ΔT c f = 333 J/g c v = kJ/mol c P,l = 4.18 J/g-K c P,s = J/g- K c P,g = J/mol- K Heat liquid… = 679 g (4.18 J / g-K ) (100 – 27.4)= 206 kJ q = +m c X Boil liquid… = mol (40.61 kJ / mol ) = 1532 kJ q = m c P ΔT Heat gas… = mol (36.76 J / mol-K ) (121.2–100)= 29.4 kJ ΔH = 1767 kJ +

With a coffee-cup calorimeter, a reaction is carried out under constant pressure conditions. -- Why is the pressure constant? calorimeter isn’t sealed, atmospheric pressure is constant -- If we assume that no heat is exchanged between the system and the surroundings, then the solution must absorb any heat given off by the reaction. -- For dilute aqueous solutions, it is a safe assumption that c P = 4.18 J/g-K the specific heat of water i.e., q absorbed = –q released